CA3224466A1 - Particulate material, method for its manufacture and use - Google Patents
Particulate material, method for its manufacture and use Download PDFInfo
- Publication number
- CA3224466A1 CA3224466A1 CA3224466A CA3224466A CA3224466A1 CA 3224466 A1 CA3224466 A1 CA 3224466A1 CA 3224466 A CA3224466 A CA 3224466A CA 3224466 A CA3224466 A CA 3224466A CA 3224466 A1 CA3224466 A1 CA 3224466A1
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- CA
- Canada
- Prior art keywords
- range
- particulate material
- nickel
- present
- combinations
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011236 particulate material Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 20
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 43
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 13
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000006182 cathode active material Substances 0.000 claims description 8
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 claims description 7
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229940000425 combination drug Drugs 0.000 claims description 2
- -1 Li2Zr03 Chemical compound 0.000 description 32
- 229920001577 copolymer Polymers 0.000 description 22
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000003570 air Substances 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 13
- 239000011777 magnesium Substances 0.000 description 13
- 239000010936 titanium Substances 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 239000011164 primary particle Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000011163 secondary particle Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 229920002239 polyacrylonitrile Polymers 0.000 description 5
- 229920001515 polyalkylene glycol Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000007669 thermal treatment Methods 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 108010062802 CD66 antigens Proteins 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- RAURUSFBVQLAPW-DNIKMYEQSA-N clocinnamox Chemical compound N1([C@@H]2CC3=CC=C(C=4O[C@@H]5[C@](C3=4)([C@]2(CCC5=O)NC(=O)\C=C\C=2C=CC(Cl)=CC=2)CC1)O)CC1CC1 RAURUSFBVQLAPW-DNIKMYEQSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 229940068917 polyethylene glycols Drugs 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 229940093470 ethylene Drugs 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 101150085274 CLEC4A gene Proteins 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 238000003109 Karl Fischer titration Methods 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000010210 aluminium Nutrition 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 235000012254 magnesium hydroxide Nutrition 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- PRJNEUBECVAVAG-UHFFFAOYSA-N 1,3-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1 PRJNEUBECVAVAG-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical group O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910007549 Li2SiF6 Inorganic materials 0.000 description 1
- 229910013462 LiC104 Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910013426 LiN(SO2F)2 Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 208000036366 Sensation of pressure Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920006373 Solef Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010416 TiO(OH)2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- ACKHWUITNXEGEP-UHFFFAOYSA-N aluminum cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Co+2].[Ni+2] ACKHWUITNXEGEP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- VTZCXKGZGDSBQC-UHFFFAOYSA-J diazanium;zirconium(4+);dicarbonate;dihydroxide Chemical compound [NH4+].[NH4+].[OH-].[OH-].[Zr+4].[O-]C([O-])=O.[O-]C([O-])=O VTZCXKGZGDSBQC-UHFFFAOYSA-J 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- YDDAAYWUOZSYKD-UHFFFAOYSA-N magnesium;aluminum;propan-2-olate Chemical compound [Mg+2].[Al].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] YDDAAYWUOZSYKD-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Inorganic materials [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N trans-Stilbene Natural products C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- OACSUWPJZKGHHK-UHFFFAOYSA-N tribenzyl phosphate Chemical compound C=1C=CC=CC=1COP(OCC=1C=CC=CC=1)(=O)OCC1=CC=CC=C1 OACSUWPJZKGHHK-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- ZMQDTYVODWKHNT-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) phosphate Chemical compound FC(F)(F)COP(=O)(OCC(F)(F)F)OCC(F)(F)F ZMQDTYVODWKHNT-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Particulate material of the composition LiaMgb)i+x(NicM1dM2e)1-xO2 wherein M1 is selected from Ti, Zr, Nb, Mo, and W, and combinations of at least two of the aforementioned, M2 is selected from Al, Co and Mn and combinations of at least two of the aforementioned, a : b is in the range of from 100:1 to 400:1, and a + b = 1, c : d is in the range of from 40:1 to 250:1, and c : e is in the range of from 12:1 to 50:1, and c + d + e = 1, total molar ratio of (Li + Mg) to (Ni + M1 + M2) is in the range of from 1 :1 to 1.05:1, 0.00 < x < 0.05, wherein said particulate material has an average particle diameter (D50) in the range of from 2 to 20 pm.
Description
Particulate material, method for its manufacture and use Specification The present invention is directed towards a particulate material of the composition (LiaMgb)i+x(NicM1dm201u x.^..2 wherein M1 is selected from Ti, Zr, Nb, Mo, and W, and combinations of at least two of the aforemen-tioned, M2 is selected from Al, Co and Mn and combinations of at least two of the aforementioned, a: b is in the range of from 100:1 to 400:1, and a + b = 1, c : d is in the range of from 40:1 to 250:1, and c: e is in the range of from 12:1 to 50:1, and c + d + e = 1, total molar ratio of (Li + Mg) to (Ni + Ml + M2) is in the range of from 1:1 to 1.05:1, 0.00 5 x 5 0.05, wherein said particulate material has an average particle diameter (D50) in the range of from
2 to 20 pm.
Lithiated transition metal oxides are currently being used as electrode active materials for lithium-ion batteries. Extensive research and developmental work has been performed in the past years to improve properties like charge density, specific energy, but also other proper-ties like the reduced cycle life and capacity loss that may adversely affect the lifetime or ap-plicability of a lithium-ion battery. Additional effort has been made to improve manufacturing methods.
Many electrode active materials discussed today are of the type of lithiated nickel-cobalt-manganese oxide ("NCM materials") or lithiated nickel-cobalt-aluminum oxide ("NCA materi-als").
In a typical process for making cathode materials for lithium-ion batteries, first a so-called precursor is being formed by co-precipitating the transition metals as carbonates, oxides or preferably as hydroxides that may or may not be basic. The precursor is then mixed with a lithium salt such as, but not limited to Li0H, Li2O or ¨ especially ¨ Li2CO3¨
and calcined (fired) at high temperatures. Lithium salt(s) can be employed as hydrate(s) or in dehydrated form. The calcination ¨ or firing ¨ generally also referred to as thermal treatment or heat treatment of the precursor ¨ is usually carried out at temperatures in the range of from 600 to 1000 C. During the thermal treatment a solid state reaction takes place, and the electrode active material is formed. In cases hydroxides or carbonates are used as precursors the solid state reaction follows a removal of water or carbon dioxide. The thermal treatment is per-formed in the heating zone of an oven or kiln.
In order to improve the capacity of cathode active materials, it has been suggested to select as high a nickel content as possible. However, in materials such as LiNi02, it has been ob-served that poor cycle life, pronounced gassing and a strong increase of the internal re-sistance during cycling provide high challenges for a commercial application.
Accordingly, the particulate material as defined at the outset has been found, hereinafter also defined as inventive material or as material according to the current invention. The inventive material shall be described in more detail below.
Inventive material has a composition according to the formula (LiaMgb)1+,(NicM1dM2e)1_x02 wherein M1 is selected from Ti, Zr, Nb, Mo, and W, and combinations of at least two of the aforemen-tioned, M2 is selected from Al, Co and Mn and combinations of at least two of the aforementioned, a: b is in the range of from 100:1 to 400:1, and a + b = 1, c : d is in the range of from 40:1 to 250:1, and c: e is in the range of from 12:1 to 50:1, and c + d + e = 1, total molar ratio of (Li + Mg) to (Ni + M1+ M2) is in the range of from 1:1 to 1.05:1, 0.00 x 0.05, wherein said particulate material has an average particle diameter (D50) in the range of from 2 to 20 pm.
Lithiated transition metal oxides are currently being used as electrode active materials for lithium-ion batteries. Extensive research and developmental work has been performed in the past years to improve properties like charge density, specific energy, but also other proper-ties like the reduced cycle life and capacity loss that may adversely affect the lifetime or ap-plicability of a lithium-ion battery. Additional effort has been made to improve manufacturing methods.
Many electrode active materials discussed today are of the type of lithiated nickel-cobalt-manganese oxide ("NCM materials") or lithiated nickel-cobalt-aluminum oxide ("NCA materi-als").
In a typical process for making cathode materials for lithium-ion batteries, first a so-called precursor is being formed by co-precipitating the transition metals as carbonates, oxides or preferably as hydroxides that may or may not be basic. The precursor is then mixed with a lithium salt such as, but not limited to Li0H, Li2O or ¨ especially ¨ Li2CO3¨
and calcined (fired) at high temperatures. Lithium salt(s) can be employed as hydrate(s) or in dehydrated form. The calcination ¨ or firing ¨ generally also referred to as thermal treatment or heat treatment of the precursor ¨ is usually carried out at temperatures in the range of from 600 to 1000 C. During the thermal treatment a solid state reaction takes place, and the electrode active material is formed. In cases hydroxides or carbonates are used as precursors the solid state reaction follows a removal of water or carbon dioxide. The thermal treatment is per-formed in the heating zone of an oven or kiln.
In order to improve the capacity of cathode active materials, it has been suggested to select as high a nickel content as possible. However, in materials such as LiNi02, it has been ob-served that poor cycle life, pronounced gassing and a strong increase of the internal re-sistance during cycling provide high challenges for a commercial application.
Accordingly, the particulate material as defined at the outset has been found, hereinafter also defined as inventive material or as material according to the current invention. The inventive material shall be described in more detail below.
Inventive material has a composition according to the formula (LiaMgb)1+,(NicM1dM2e)1_x02 wherein M1 is selected from Ti, Zr, Nb, Mo, and W, and combinations of at least two of the aforemen-tioned, M2 is selected from Al, Co and Mn and combinations of at least two of the aforementioned, a: b is in the range of from 100:1 to 400:1, and a + b = 1, c : d is in the range of from 40:1 to 250:1, and c: e is in the range of from 12:1 to 50:1, and c + d + e = 1, total molar ratio of (Li + Mg) to (Ni + M1+ M2) is in the range of from 1:1 to 1.05:1, 0.00 x 0.05, wherein said particulate material has an average particle diameter (D50) in the range of from 2 to 20 pm.
3 This corresponds to the formula (Li Ma 1 TM 10 wherein TM is (Nii-x1-x2 =aõb,1+x- ¨1-x-2 M1x1M2x2) with x1 0.0025 and x2 0.05 and x1 + x2 s 0.0525.
The inventive material will be described in more detail below.
In one embodiment of the present invention, inventive material is comprised of spherical par-ticles, that are particles having a spherical shape. Spherical particles shall include not just those which are exactly spherical but also those particles in which the maximum and mini-mum diameter of at least 90% (number average) of a representative sample differ by not more than 10%.
The inventive material has an average particle diameter (D50) in the range of from 2 to 20 pm, preferably from 5 to 16 pm. The average particle diameter can be determined, e. g., by light scattering or LASER diffraction or electroacoustic spectroscopy. The particles are usual-ly composed of agglomerates from primary particles, and the above particle diameter refers to the secondary particle diameter.
In one embodiment of the present invention, the inventive material is comprised of secondary particles that are agglomerates of primary particles. Preferably, the inventive material is comprised of spherical secondary particles that are agglomerates of primary particles. Even more preferably, inventive material is comprised of spherical secondary particles that are agglomerates of spherical primary particles or platelets.
In one embodiment of the present invention, primary particles of inventive material have an average diameter in the range from Ito 2000 nm, preferably from 10 to 1000 nm, particularly preferably from 50 to 500 nm. The average primary particle diameter can, for example, be determined by SEM or TEM. SEM is an abbreviation of scanning electron microscopy, TEM
is an abbreviation of transmission electron microscopy, and XRD stands for X-ray diffraction.
In one embodiment of the present invention, the inventive material has a specific surface (BET), hereinafter also referred to as "BET surface", in the range of from 0.1 to 2.0 m2/g. The BET surface may be determined by nitrogen adsorption after outgassing of the sample at 200 C for 30 minutes or more and beyond this in accordance with DIN ISO
9277:2010.
M1 is selected from Ti, Zr, Nb, Mo, and W, and combinations of at least two of the aforemen-tioned, preferably M1 is selected from combinations of at least two of Ti, Zr, Nb, Mo, and W,
The inventive material will be described in more detail below.
In one embodiment of the present invention, inventive material is comprised of spherical par-ticles, that are particles having a spherical shape. Spherical particles shall include not just those which are exactly spherical but also those particles in which the maximum and mini-mum diameter of at least 90% (number average) of a representative sample differ by not more than 10%.
The inventive material has an average particle diameter (D50) in the range of from 2 to 20 pm, preferably from 5 to 16 pm. The average particle diameter can be determined, e. g., by light scattering or LASER diffraction or electroacoustic spectroscopy. The particles are usual-ly composed of agglomerates from primary particles, and the above particle diameter refers to the secondary particle diameter.
In one embodiment of the present invention, the inventive material is comprised of secondary particles that are agglomerates of primary particles. Preferably, the inventive material is comprised of spherical secondary particles that are agglomerates of primary particles. Even more preferably, inventive material is comprised of spherical secondary particles that are agglomerates of spherical primary particles or platelets.
In one embodiment of the present invention, primary particles of inventive material have an average diameter in the range from Ito 2000 nm, preferably from 10 to 1000 nm, particularly preferably from 50 to 500 nm. The average primary particle diameter can, for example, be determined by SEM or TEM. SEM is an abbreviation of scanning electron microscopy, TEM
is an abbreviation of transmission electron microscopy, and XRD stands for X-ray diffraction.
In one embodiment of the present invention, the inventive material has a specific surface (BET), hereinafter also referred to as "BET surface", in the range of from 0.1 to 2.0 m2/g. The BET surface may be determined by nitrogen adsorption after outgassing of the sample at 200 C for 30 minutes or more and beyond this in accordance with DIN ISO
9277:2010.
M1 is selected from Ti, Zr, Nb, Mo, and W, and combinations of at least two of the aforemen-tioned, preferably M1 is selected from combinations of at least two of Ti, Zr, Nb, Mo, and W,
4 for example combinations of Ti and Zr or combinations of Zr and Mo or combinations of Ti and Zr and Mo.
M2 is selected from Al, Co and Mn and combinations of at least two of the aforementioned, a: b is in the range of from 100:1 to 400:1, and a + b = 1, c : d is in the range of from 40:1 to 250:1, and c: e is in the range of from 12:1 to 50:1, and c + d + e = 1, total molar ratio of (Li + Mg) to (Ni + M1+ M2) is in the range of from 1:1 to 1.05:1, 0.00 s x s 0.05, Some metals are ubiquitous metals such as sodium, calcium or zinc, but such traces will not be taken into account in the description of the present invention. Traces in this context will mean amounts of 0.05 mol-% or less, referring to the total metal content TM.
Preferably, the calcium content of inventive material is only traces, and no compound of calcium is deliber-ately added during manufacture.
In one embodiment of the present invention, said material comprises a combination of metals according to formula (I) (NicM1dM2e) (I) with M2 being selected from Mn and Co, c being in the range of from 0.95 to 0.995, d being in the range of from 0.002 to 0.04, e being in the range of from 0.002 to 0.02, and c + d + e = 1. In a preferred embodiment, b S c.
M1 is selected from Nb, Ti, Zr, W, and Mo and preferably from combinations of at least two of the aforementioned, and M2 is selected from Al, Mn, and Co and combinations of at least two of the aforementioned.
M2 is selected from Al, Co and Mn and combinations of at least two of the aforementioned, a: b is in the range of from 100:1 to 400:1, and a + b = 1, c : d is in the range of from 40:1 to 250:1, and c: e is in the range of from 12:1 to 50:1, and c + d + e = 1, total molar ratio of (Li + Mg) to (Ni + M1+ M2) is in the range of from 1:1 to 1.05:1, 0.00 s x s 0.05, Some metals are ubiquitous metals such as sodium, calcium or zinc, but such traces will not be taken into account in the description of the present invention. Traces in this context will mean amounts of 0.05 mol-% or less, referring to the total metal content TM.
Preferably, the calcium content of inventive material is only traces, and no compound of calcium is deliber-ately added during manufacture.
In one embodiment of the present invention, said material comprises a combination of metals according to formula (I) (NicM1dM2e) (I) with M2 being selected from Mn and Co, c being in the range of from 0.95 to 0.995, d being in the range of from 0.002 to 0.04, e being in the range of from 0.002 to 0.02, and c + d + e = 1. In a preferred embodiment, b S c.
M1 is selected from Nb, Ti, Zr, W, and Mo and preferably from combinations of at least two of the aforementioned, and M2 is selected from Al, Mn, and Co and combinations of at least two of the aforementioned.
5 In one embodiment of the present invention, M1 is selected from Ti, Zr and W, and combina-tions of two of the aforementioned.
In one embodiment of the present invention the number of metals other than Ni, Mg and Li is at least three and at most five. More preferably, only one element M2 is present.
In one embodiment of the present invention, metal(s) M1 is/are each present in a molar per-centage with reference to Ni in the range of from 0.1 to 0.5.
In one embodiment of the present invention, metal(s) M2 are each present in a molar per-centage with reference to Ni in the range of from 0.5 to 2.
In one embodiment of the present invention, M1 and M2 are homogeneously dispersed within the inventive material. That means that M1 and M2 are about uniformly distributed over the particles of inventive material.
In one embodiment of the present invention, at least one of M1 and M2 are enriched in the particle boundaries of particles of inventive material.
In a specific embodiment of the present invention, secondary particles of inventive material are coated with a metal oxide, preferably with a metal oxide that does not serve as a cathode active material. Examples of suitable metal oxides are LiB02, B203, A1203, Y203, LiA102, TiO2, ZrO2, Li2Zr03, Nb2O5, and LiNb03.
Inventive materials are particularly suitable as cathode active materials for lithium ion batter-ies. They combine good cycling stability with a high energy density.
In one embodiment of the present invention inventive cathode active material contains in the range of from 0.001 to 1 % by weight Li2CO3, determined by titration as Li2CO3 and referring to said inventive material.
Another aspect of the present invention relates to a process for making inventive materials, hereinafter also referred to as inventive process or process according to the (present) inven-tion. The inventive process comprises several steps, hereinafter also referred to as step (a), step (b) etc.
In one embodiment of the present invention the number of metals other than Ni, Mg and Li is at least three and at most five. More preferably, only one element M2 is present.
In one embodiment of the present invention, metal(s) M1 is/are each present in a molar per-centage with reference to Ni in the range of from 0.1 to 0.5.
In one embodiment of the present invention, metal(s) M2 are each present in a molar per-centage with reference to Ni in the range of from 0.5 to 2.
In one embodiment of the present invention, M1 and M2 are homogeneously dispersed within the inventive material. That means that M1 and M2 are about uniformly distributed over the particles of inventive material.
In one embodiment of the present invention, at least one of M1 and M2 are enriched in the particle boundaries of particles of inventive material.
In a specific embodiment of the present invention, secondary particles of inventive material are coated with a metal oxide, preferably with a metal oxide that does not serve as a cathode active material. Examples of suitable metal oxides are LiB02, B203, A1203, Y203, LiA102, TiO2, ZrO2, Li2Zr03, Nb2O5, and LiNb03.
Inventive materials are particularly suitable as cathode active materials for lithium ion batter-ies. They combine good cycling stability with a high energy density.
In one embodiment of the present invention inventive cathode active material contains in the range of from 0.001 to 1 % by weight Li2CO3, determined by titration as Li2CO3 and referring to said inventive material.
Another aspect of the present invention relates to a process for making inventive materials, hereinafter also referred to as inventive process or process according to the (present) inven-tion. The inventive process comprises several steps, hereinafter also referred to as step (a), step (b) etc.
6 Steps (a) to (c) are characterized as follows:
(a) providing a particulate nickel hydroxide, nickel (II) oxide or nickel oxyhydroxide, (b) mixing said nickel oxide/hydroxide with compounds of Mg, of M1 and M2, in the ab-sence of solvent, and with a source of lithium, (c) treating the mixture obtained from step (b) thermally.
Steps (a) to (c) are described in more detail below.
In step (a), a particulate nickel hydroxide, nickel (II) oxide or nickel oxyhydroxide is provided, hereinafter altogether also referred to as nickel oxide/hydroxide. In the context of the present invention, the term nickel oxyhydroxide is not limited to stoichiometric Ni0OH
but to any compound of nickel that bears only oxide and hydroxide counterions and a maximum individ-ual content of impurities of 2% by weight of metals such as Mn or Mg, referring to the total metal content of said nickel hydroxide, nickel (II) oxide or nickel oxyhydroxide. Preferably, nickel hydroxide, nickel (II) oxide or nickel oxyhydroxide has a maximum total impurity con-tent of 2% by weight, referring to the total metal content of said nickel hydroxide, nickel (II) oxide or nickel oxyhydroxide.
The nickel oxide/hydroxide provided in step (a) has an average particle diameter (D50) in the range of from 2 to 20 pm, preferably from 4 to 16 pm. The average particle diameter can be determined, e. g., by light scattering or LASER diffraction or electroacoustic spectroscopy.
The particles may be composed of agglomerates from primary particles, and the above parti-cle diameter refers to the secondary particle diameter.
A preferred nickel oxide/hydroxide is freshly precipitated nickel hydroxide.
In one embodiment of the present invention, the nickel oxide/hydroxide provided in step (a) has a residual moisture content in the range of from 50 to 1,000 ppm, preferably from 100 to 400 ppm. The residual moisture content may be determined by Karl-Fischer titration.
In step (b), said nickel oxide/hydroxide is mixed with compounds of Mg and M1 and M2, in the absence of solvents such as water or organic solvents.
Suitable compounds of Mg are Mg(OH)2, MgO, Mg(NO3)2, and oxalates such as MgC204.
(a) providing a particulate nickel hydroxide, nickel (II) oxide or nickel oxyhydroxide, (b) mixing said nickel oxide/hydroxide with compounds of Mg, of M1 and M2, in the ab-sence of solvent, and with a source of lithium, (c) treating the mixture obtained from step (b) thermally.
Steps (a) to (c) are described in more detail below.
In step (a), a particulate nickel hydroxide, nickel (II) oxide or nickel oxyhydroxide is provided, hereinafter altogether also referred to as nickel oxide/hydroxide. In the context of the present invention, the term nickel oxyhydroxide is not limited to stoichiometric Ni0OH
but to any compound of nickel that bears only oxide and hydroxide counterions and a maximum individ-ual content of impurities of 2% by weight of metals such as Mn or Mg, referring to the total metal content of said nickel hydroxide, nickel (II) oxide or nickel oxyhydroxide. Preferably, nickel hydroxide, nickel (II) oxide or nickel oxyhydroxide has a maximum total impurity con-tent of 2% by weight, referring to the total metal content of said nickel hydroxide, nickel (II) oxide or nickel oxyhydroxide.
The nickel oxide/hydroxide provided in step (a) has an average particle diameter (D50) in the range of from 2 to 20 pm, preferably from 4 to 16 pm. The average particle diameter can be determined, e. g., by light scattering or LASER diffraction or electroacoustic spectroscopy.
The particles may be composed of agglomerates from primary particles, and the above parti-cle diameter refers to the secondary particle diameter.
A preferred nickel oxide/hydroxide is freshly precipitated nickel hydroxide.
In one embodiment of the present invention, the nickel oxide/hydroxide provided in step (a) has a residual moisture content in the range of from 50 to 1,000 ppm, preferably from 100 to 400 ppm. The residual moisture content may be determined by Karl-Fischer titration.
In step (b), said nickel oxide/hydroxide is mixed with compounds of Mg and M1 and M2, in the absence of solvents such as water or organic solvents.
Suitable compounds of Mg are Mg(OH)2, MgO, Mg(NO3)2, and oxalates such as MgC204.
7 Suitable compounds of M1 are oxides, (oxy)hydroxides and nitrates of Ti, of Zr, of W, of Mo, and of Nb, such as TiO2, Ti203, TiO(OH)2, ZrO2, Zr(OH)4, TiO(NO3)2, Ti(NO3)4, niobic acid, Nb2O5, W03, Li2W04, and Mo03. Further examples of compounds of M1 are for instance but not limited to ammonium metatungstate (hydrate), ammonium orthomolybdate, ammonium heptamolybdate, ammonium dimolybdate, ammonium niobate oxalate, ammonium zirconium (IV) carbonate, either as such or as hydrates.
Suitable compounds of M2 are nitrates, oxides, hydroxides and oxyhydroxides, for example A1203, Al(OH)3, A100H, Al2(SO4)3, KAI(SO4)2, and Al(NO3)3, alkanolates of Al such as, but not limited to Al(C21-150)3, Al-tris-isopropoxide, mixed salts of at least 2 cations such as alu-minum magnesium isopropoxide. Examples of compound of cobalt are Co(OH)2, Co203, Co304, and examples of compounds of Mn are Mn203, Mn02, and Mn(NO3)2.
Alkanolates of M2 are possible as well.
In addition, a source of lithium is added.
Examples of sources of lithium are Li2O, Li0H, and Li2CO3, each water-free or as hydrate, if applicable, for example Li0H-1-120. Preferred example is lithium hydroxide.
The amounts of source of lithium and of powdery residue is selected in a way that the molar ratio of Li and TM is (1+x) to 1, with x being in the range of from 0.98 to 1.05.
Said source of lithium is preferable in particulate form, for example with an average diameter (D50) in the range of from 3 to 10 pm, preferably from 5 to 9 pm.
In one embodiment of the present invention, step (b) is performed at a temperature in the range of from 5 to 85 C, preferred are 10 to 60 C.
In one embodiment of the present invention, step (b) is performed at normal pressure. It is preferred, though, to perform step (b) under elevated pressure, for example at 10 mbar to 10 bar above normal pressure, or with suction, for example 50 to 250 mbar below normal pres-sure, preferably 100 to 200 mbar below normal pressure.
Step (b) may be performed, for example, in a vessel that can be easily discharged, for ex-ample due to its location above a filter device. Such vessel may be charged with nickel ox-ide/hydroxide from step (a) followed by introduction of source of lithium and of compounds of Mg and M1 and M2. In another embodiment, such vessel is charged with source of lithium
Suitable compounds of M2 are nitrates, oxides, hydroxides and oxyhydroxides, for example A1203, Al(OH)3, A100H, Al2(SO4)3, KAI(SO4)2, and Al(NO3)3, alkanolates of Al such as, but not limited to Al(C21-150)3, Al-tris-isopropoxide, mixed salts of at least 2 cations such as alu-minum magnesium isopropoxide. Examples of compound of cobalt are Co(OH)2, Co203, Co304, and examples of compounds of Mn are Mn203, Mn02, and Mn(NO3)2.
Alkanolates of M2 are possible as well.
In addition, a source of lithium is added.
Examples of sources of lithium are Li2O, Li0H, and Li2CO3, each water-free or as hydrate, if applicable, for example Li0H-1-120. Preferred example is lithium hydroxide.
The amounts of source of lithium and of powdery residue is selected in a way that the molar ratio of Li and TM is (1+x) to 1, with x being in the range of from 0.98 to 1.05.
Said source of lithium is preferable in particulate form, for example with an average diameter (D50) in the range of from 3 to 10 pm, preferably from 5 to 9 pm.
In one embodiment of the present invention, step (b) is performed at a temperature in the range of from 5 to 85 C, preferred are 10 to 60 C.
In one embodiment of the present invention, step (b) is performed at normal pressure. It is preferred, though, to perform step (b) under elevated pressure, for example at 10 mbar to 10 bar above normal pressure, or with suction, for example 50 to 250 mbar below normal pres-sure, preferably 100 to 200 mbar below normal pressure.
Step (b) may be performed, for example, in a vessel that can be easily discharged, for ex-ample due to its location above a filter device. Such vessel may be charged with nickel ox-ide/hydroxide from step (a) followed by introduction of source of lithium and of compounds of Mg and M1 and M2. In another embodiment, such vessel is charged with source of lithium
8 and with compounds of Mg and M1 and M2 followed by introduction of nickel oxide/hydroxide from step (a). In another embodiment, nickel oxide/hydroxide from step (a) and compounds of Mg and M1 and M2 and source of lithium are introduced simultaneously.
Mixing of the nickel oxide/hydroxide with the compounds of Mg and M1 and M2 and the source of lithium may take place over a period of from 1 minute to 3 hours, preferably from 5 minutes to 1 hour, even more preferably from 5 to 30 minutes.
Step (b) may be supported by mixing operations, for example shaking or in particular by stir-ring or shearing, see below.
A powdery mixture is obtained from step (b).
Examples of suitable apparatuses for performing step (b) are high-shear mixers, tumbler mixers, plough-share mixers and free fall mixers.
In one embodiment of the present invention, step (b) is performed at a temperature in the range of from ambient temperature to 200 C, preferably 20 to 50 C.
A mixture is obtained.
Step (c) includes subjecting said mixture from step (b) to a thermal treatment. Examples of step (c) are heat treatments at a temperature in the range of from 600 to 800 C, preferably 650 to 750 C. The terms "treating thermally" and "heat treatment" are used interchangeably in the context of the present invention.
In one embodiment of the present invention, the mixture obtained from step (b) is heated to 600 to 800 C with a heating rate of 0.1 to 10 C/min.
In one embodiment of the present invention, the temperature is ramped up before reaching the desired temperature of from 600 to 800 C, preferably 650 to 750 C. For example, first the mixture obtained from step (c) is heated to a temperature to 350 to 550 C
and then held constant for a time of 10 min to 4 hours, and then it is raised to 650 C up to 800 C and then held at 650 to 800 for 10 minutes to 10 hours.
In one embodiment of the present invention, step (c) is performed in a roller hearth kiln, a pusher kiln or a rotary kiln or a combination of at least two of the foregoing. Rotary kilns have
Mixing of the nickel oxide/hydroxide with the compounds of Mg and M1 and M2 and the source of lithium may take place over a period of from 1 minute to 3 hours, preferably from 5 minutes to 1 hour, even more preferably from 5 to 30 minutes.
Step (b) may be supported by mixing operations, for example shaking or in particular by stir-ring or shearing, see below.
A powdery mixture is obtained from step (b).
Examples of suitable apparatuses for performing step (b) are high-shear mixers, tumbler mixers, plough-share mixers and free fall mixers.
In one embodiment of the present invention, step (b) is performed at a temperature in the range of from ambient temperature to 200 C, preferably 20 to 50 C.
A mixture is obtained.
Step (c) includes subjecting said mixture from step (b) to a thermal treatment. Examples of step (c) are heat treatments at a temperature in the range of from 600 to 800 C, preferably 650 to 750 C. The terms "treating thermally" and "heat treatment" are used interchangeably in the context of the present invention.
In one embodiment of the present invention, the mixture obtained from step (b) is heated to 600 to 800 C with a heating rate of 0.1 to 10 C/min.
In one embodiment of the present invention, the temperature is ramped up before reaching the desired temperature of from 600 to 800 C, preferably 650 to 750 C. For example, first the mixture obtained from step (c) is heated to a temperature to 350 to 550 C
and then held constant for a time of 10 min to 4 hours, and then it is raised to 650 C up to 800 C and then held at 650 to 800 for 10 minutes to 10 hours.
In one embodiment of the present invention, step (c) is performed in a roller hearth kiln, a pusher kiln or a rotary kiln or a combination of at least two of the foregoing. Rotary kilns have
9 the advantage of a very good homogenization of the material made therein. In roller hearth kilns and in pusher kilns, different reaction conditions with respect to different steps may be set quite easily. In lab scale trials, box-type and tubular furnaces and split tube furnaces are feasible as well.
In one embodiment of the present invention, step (c) is performed in an oxygen-containing atmosphere, for example in a nitrogen-air mixture, in a rare gas-oxygen mixture, in air, in oxygen or in oxygen-enriched air. In a preferred embodiment, the atmosphere in step (c) is selected from air, oxygen and oxygen-enriched air. Oxygen-enriched air may be, for exam-ple, a 50:50 by volume mix of air and oxygen. Other options are 1:2 by volume mixtures of air and oxygen, 1:3 by volume mixtures of air and oxygen, 2:1 by volume mixtures of air and oxygen, and 3:1 by volume mixtures of air and oxygen.
In one embodiment of the present invention, step (c) is performed under a stream of gas, for example air, oxygen and oxygen-enriched air. Such stream of gas may be termed a forced gas flow. Such stream of gas may have a specific flow rate in the range of from 0.5 to 15 m3/h=kg material according to general formula (LialAgb)1+x(NicMidm201 xk.) =-s2. The volume is de-termined under normal conditions: 298 Kelvin and 1 atmosphere. Said stream of gas is use-ful for removal of gaseous cleavage products such as water and carbon dioxide.
The inventive process may include further steps such as, but not limited, additional calcina-tion steps at a temperature in the range of from 650 to 800 C subsequently to step (c).
In one embodiment of the present invention, step (c) has a duration in the range of from one hour to 30 hours. Preferred are 10 to 24 hours. The time at a temperature above 600 C is counted, heating and holding but the cooling time is neglected in this context.
A material is obtained that is excellently suitable as cathode active material for lithium ion batteries.
In one embodiment of the present invention, it is possible to treat inventive material with wa-ter and subsequently drying it. In another embodiment, it is possible to at least partially coat particles of inventive material, for example by mixing it with an oxide or hydroxide, for exam-ple with aluminum hydroxide or alumina or with boric acid, followed by thermal treatment at 150 to 400 C. In another embodiment of the present invention, it is possible to at least par-tially coat particles of inventive material by way of atomic layer deposition methods, for ex-ample by alternating treatment(s) with trimethylaluminum and moisture.
In one embodiment of the present invention, step (c) is performed in an oxygen-containing atmosphere, for example in a nitrogen-air mixture, in a rare gas-oxygen mixture, in air, in oxygen or in oxygen-enriched air. In a preferred embodiment, the atmosphere in step (c) is selected from air, oxygen and oxygen-enriched air. Oxygen-enriched air may be, for exam-ple, a 50:50 by volume mix of air and oxygen. Other options are 1:2 by volume mixtures of air and oxygen, 1:3 by volume mixtures of air and oxygen, 2:1 by volume mixtures of air and oxygen, and 3:1 by volume mixtures of air and oxygen.
In one embodiment of the present invention, step (c) is performed under a stream of gas, for example air, oxygen and oxygen-enriched air. Such stream of gas may be termed a forced gas flow. Such stream of gas may have a specific flow rate in the range of from 0.5 to 15 m3/h=kg material according to general formula (LialAgb)1+x(NicMidm201 xk.) =-s2. The volume is de-termined under normal conditions: 298 Kelvin and 1 atmosphere. Said stream of gas is use-ful for removal of gaseous cleavage products such as water and carbon dioxide.
The inventive process may include further steps such as, but not limited, additional calcina-tion steps at a temperature in the range of from 650 to 800 C subsequently to step (c).
In one embodiment of the present invention, step (c) has a duration in the range of from one hour to 30 hours. Preferred are 10 to 24 hours. The time at a temperature above 600 C is counted, heating and holding but the cooling time is neglected in this context.
A material is obtained that is excellently suitable as cathode active material for lithium ion batteries.
In one embodiment of the present invention, it is possible to treat inventive material with wa-ter and subsequently drying it. In another embodiment, it is possible to at least partially coat particles of inventive material, for example by mixing it with an oxide or hydroxide, for exam-ple with aluminum hydroxide or alumina or with boric acid, followed by thermal treatment at 150 to 400 C. In another embodiment of the present invention, it is possible to at least par-tially coat particles of inventive material by way of atomic layer deposition methods, for ex-ample by alternating treatment(s) with trimethylaluminum and moisture.
10 A further aspect of the present invention are electrodes comprising at least one inventive material. They are particularly useful for lithium ion batteries. Lithium ion batteries comprising at least one electrode according to the present invention exhibit a very good discharge and cycling behavior, and they show good safety behavior.
In one embodiment of the present invention, inventive cathodes contain (A) at least one inventive material, as described above, (B) carbon in an electrically conductive state, and (C) a binder, (D) a current collector.
In a preferred embodiment of the present invention, inventive cathodes contain (A) 80 to 98 % by weight inventive material, (B) Ito 17% by weight of carbon, (C) Ito 10 % by weight of binder material, percentages referring to the sum of (A), (B) and (C).
Cathodes according to the present invention contain carbon in electrically conductive modifi-cation, in brief also referred to as carbon (B). Carbon (B) can be selected from soot, active carbon, carbon nanotubes, graphene, and graphite. Carbon (B) can be added as such during preparation of electrode materials according to the invention.
Electrodes according to the present invention can comprise further components.
They can comprise a current collector (D), such as, but not limited to, an aluminum foil. They further comprise a binder material (C), hereinafter also referred to as binder (C).
Current collector (D) is not further described here.
Suitable binders (C) are preferably selected from organic (co)polymers.
Suitable (co)polymers, i.e. homopolymers or copolymers, can be selected, for example, from (co)polymers obtainable by anionic, catalytic or free-radical (co)polymerization, especially from polyethylene, polyacrylonitrile, polybutadiene, polystyrene, and copolymers of at least two comonomers selected from ethylene, propylene, styrene, (meth)acrylonitrile and 1,3-butadiene. Polypropylene is also suitable. Polyisoprene and polyacrylates are additionally suitable. Particular preference is given to polyacrylonitrile.
In one embodiment of the present invention, inventive cathodes contain (A) at least one inventive material, as described above, (B) carbon in an electrically conductive state, and (C) a binder, (D) a current collector.
In a preferred embodiment of the present invention, inventive cathodes contain (A) 80 to 98 % by weight inventive material, (B) Ito 17% by weight of carbon, (C) Ito 10 % by weight of binder material, percentages referring to the sum of (A), (B) and (C).
Cathodes according to the present invention contain carbon in electrically conductive modifi-cation, in brief also referred to as carbon (B). Carbon (B) can be selected from soot, active carbon, carbon nanotubes, graphene, and graphite. Carbon (B) can be added as such during preparation of electrode materials according to the invention.
Electrodes according to the present invention can comprise further components.
They can comprise a current collector (D), such as, but not limited to, an aluminum foil. They further comprise a binder material (C), hereinafter also referred to as binder (C).
Current collector (D) is not further described here.
Suitable binders (C) are preferably selected from organic (co)polymers.
Suitable (co)polymers, i.e. homopolymers or copolymers, can be selected, for example, from (co)polymers obtainable by anionic, catalytic or free-radical (co)polymerization, especially from polyethylene, polyacrylonitrile, polybutadiene, polystyrene, and copolymers of at least two comonomers selected from ethylene, propylene, styrene, (meth)acrylonitrile and 1,3-butadiene. Polypropylene is also suitable. Polyisoprene and polyacrylates are additionally suitable. Particular preference is given to polyacrylonitrile.
11 In the context of the present invention, polyacrylonitrile is understood to mean not only poly-acrylonitrile homopolymers but also copolymers of acrylonitrile with 1,3-butadiene or styrene.
Preference is given to polyacrylonitrile homopolymers.
In the context of the present invention, polyethylene is not only understood to mean honno-polyethylene, but also copolymers of ethylene which comprise at least 50 mol%
of copoly-merized ethylene and up to 50 mol% of at least one further comonomer, for example a-olefins such as propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, and also isobutene, vinylaronnatics, for example styrene, and also (meth)acrylic acid, vinyl acetate, vinyl propionate, C1-C10-alkyl esters of (meth)acrylic acid, especially methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and also ma-leic acid, maleic anhydride and itaconic anhydride. Polyethylene may be HDPE
or LDPE.
In the context of the present invention, polypropylene is not only understood to mean homo-polypropylene, but also copolymers of propylene which comprise at least 50 mol% of copol-ymerized propylene and up to 50 mol% of at least one further connonomer, for example eth-ylene and a-olefins such as butylene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-pentene. Polypropylene is preferably isotactic or essentially isotactic polypropylene.
In the context of the present invention, polystyrene is not only understood to mean homopol-ymers of styrene, but also copolymers with acrylonitrile, 1,3-butadiene, (meth)acrylic acid, Ci-Cio-alkyl esters of (meth)acrylic acid, divinylbenzene, especially 1,3-divinylbenzene, 1,2-diphenylethylene and a-methylstyrene.
Another preferred binder (C) is polybutadiene.
Other suitable binders (C) are selected from polyethylene oxide (PEO), cellulose, carbox-ymethylcellulose, polyimides and polyvinyl alcohol.
In one embodiment of the present invention, binder (C) is selected from those (co)polymers which have an average molecular weight Mw in the range from 50,000 to 1,000,000 g/mol, preferably to 500,000 g/mol.
Binder (C) may be cross-linked or non-cross-linked (co)polymers.
Preference is given to polyacrylonitrile homopolymers.
In the context of the present invention, polyethylene is not only understood to mean honno-polyethylene, but also copolymers of ethylene which comprise at least 50 mol%
of copoly-merized ethylene and up to 50 mol% of at least one further comonomer, for example a-olefins such as propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, and also isobutene, vinylaronnatics, for example styrene, and also (meth)acrylic acid, vinyl acetate, vinyl propionate, C1-C10-alkyl esters of (meth)acrylic acid, especially methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and also ma-leic acid, maleic anhydride and itaconic anhydride. Polyethylene may be HDPE
or LDPE.
In the context of the present invention, polypropylene is not only understood to mean homo-polypropylene, but also copolymers of propylene which comprise at least 50 mol% of copol-ymerized propylene and up to 50 mol% of at least one further connonomer, for example eth-ylene and a-olefins such as butylene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-pentene. Polypropylene is preferably isotactic or essentially isotactic polypropylene.
In the context of the present invention, polystyrene is not only understood to mean homopol-ymers of styrene, but also copolymers with acrylonitrile, 1,3-butadiene, (meth)acrylic acid, Ci-Cio-alkyl esters of (meth)acrylic acid, divinylbenzene, especially 1,3-divinylbenzene, 1,2-diphenylethylene and a-methylstyrene.
Another preferred binder (C) is polybutadiene.
Other suitable binders (C) are selected from polyethylene oxide (PEO), cellulose, carbox-ymethylcellulose, polyimides and polyvinyl alcohol.
In one embodiment of the present invention, binder (C) is selected from those (co)polymers which have an average molecular weight Mw in the range from 50,000 to 1,000,000 g/mol, preferably to 500,000 g/mol.
Binder (C) may be cross-linked or non-cross-linked (co)polymers.
12 In a particularly preferred embodiment of the present invention, binder (C) is selected from halogenated (co)polymers, especially from fluorinated (co)polymers.
Halogenated or fluori-nated (co)polymers are understood to mean those (co)polymers which comprise at least one (co)polymerized (co)monomer which has at least one halogen atom or at least one fluorine atom per molecule, more preferably at least two halogen atoms or at least two fluorine atoms per molecule. Examples are polyvinyl chloride, polyvinylidene chloride, polytetrafluoroeth-ylene, polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers and ethylene-chlorofluoroethylene copolymers.
Suitable binders (C) are especially polyvinyl alcohol and halogenated (co)polymers, for ex-ample polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvinyl fluoride and especially polyvinylidene fluoride and polytetrafluoroethylene.
Inventive electrodes may comprise 3 to 10% by weight of binder(s) (d), referring to the sum of component (a), component (b) and carbon (c).
A further aspect of the present invention is a battery, containing (A) at least one cathode comprising inventive cathode active material (A), carbon (B), and binder (C), (B) at least one anode, and (C) at least one electrolyte.
Embodiments of cathode (1) have been described above in detail.
Anode (2) may contain at least one anode active material, such as carbon (graphite), h02, lithium titanium oxide, silicon or tin. Anode (2) may additionally contain a current collector, for example a metal foil such as a copper foil.
Electrolyte (3) may comprise at least one non-aqueous solvent, at least one electrolyte salt and, optionally, additives.
Halogenated or fluori-nated (co)polymers are understood to mean those (co)polymers which comprise at least one (co)polymerized (co)monomer which has at least one halogen atom or at least one fluorine atom per molecule, more preferably at least two halogen atoms or at least two fluorine atoms per molecule. Examples are polyvinyl chloride, polyvinylidene chloride, polytetrafluoroeth-ylene, polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers and ethylene-chlorofluoroethylene copolymers.
Suitable binders (C) are especially polyvinyl alcohol and halogenated (co)polymers, for ex-ample polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvinyl fluoride and especially polyvinylidene fluoride and polytetrafluoroethylene.
Inventive electrodes may comprise 3 to 10% by weight of binder(s) (d), referring to the sum of component (a), component (b) and carbon (c).
A further aspect of the present invention is a battery, containing (A) at least one cathode comprising inventive cathode active material (A), carbon (B), and binder (C), (B) at least one anode, and (C) at least one electrolyte.
Embodiments of cathode (1) have been described above in detail.
Anode (2) may contain at least one anode active material, such as carbon (graphite), h02, lithium titanium oxide, silicon or tin. Anode (2) may additionally contain a current collector, for example a metal foil such as a copper foil.
Electrolyte (3) may comprise at least one non-aqueous solvent, at least one electrolyte salt and, optionally, additives.
13 Nonaqueous solvents for electrolyte (3) can be liquid or solid at room temperature and is preferably selected from among polymers, cyclic or acyclic ethers, cyclic and acyclic acetals and cyclic or acyclic organic carbonates.
Examples of suitable polymers are, in particular, polyalkylene glycols, preferably poly-Ci-C4-alkylene glycols and in particular polyethylene glycols. Polyethylene glycols can here com-prise up to 20 mol% of one or more Ci-C4-alkylene glycols. Polyalkylene glycols are prefera-bly polyalkylene glycols having two methyl or ethyl end caps.
The molecular weight Mw of suitable polyalkylene glycols and in particular suitable polyeth-ylene glycols can be at least 400 g/mol.
The molecular weight Mw of suitable polyalkylene glycols and in particular suitable polyeth-ylene glycols can be up to 5,000,000 g/mol, preferably up to 2,000,000 g/mol.
Examples of suitable acyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, with preference being given to 1,2-dimethoxyethane.
Examples of suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.
Examples of suitable acyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane and 1,1-diethoxyethane.
Examples of suitable cyclic acetals are 1,3-dioxane and in particular 1,3-dioxolane.
Examples of suitable acyclic organic carbonates are dimethyl carbonate, ethyl methyl car-bonate and diethyl carbonate.
Examples of suitable polymers are, in particular, polyalkylene glycols, preferably poly-Ci-C4-alkylene glycols and in particular polyethylene glycols. Polyethylene glycols can here com-prise up to 20 mol% of one or more Ci-C4-alkylene glycols. Polyalkylene glycols are prefera-bly polyalkylene glycols having two methyl or ethyl end caps.
The molecular weight Mw of suitable polyalkylene glycols and in particular suitable polyeth-ylene glycols can be at least 400 g/mol.
The molecular weight Mw of suitable polyalkylene glycols and in particular suitable polyeth-ylene glycols can be up to 5,000,000 g/mol, preferably up to 2,000,000 g/mol.
Examples of suitable acyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, with preference being given to 1,2-dimethoxyethane.
Examples of suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.
Examples of suitable acyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane and 1,1-diethoxyethane.
Examples of suitable cyclic acetals are 1,3-dioxane and in particular 1,3-dioxolane.
Examples of suitable acyclic organic carbonates are dimethyl carbonate, ethyl methyl car-bonate and diethyl carbonate.
14 Examples of suitable cyclic organic carbonates are compounds of the general formulae (II) and (111) .7.
___________________________________________ R (II) R1) (R2 3 /\
(III) R
where R1, R2 and R3 can be identical or different and are selected from among hydrogen and C1-C4-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, with R2 and R3 preferably not both being tert-butyl.
In particularly preferred embodiments, R1 is methyl and R2 and R3 are each hydrogen, or R1, R2 and R3 are each hydrogen.
Another preferred cyclic organic carbonate is vinylene carbonate, formula (IV).
V\
\¨/ (IV) The solvent or solvents is/are preferably used in the water-free state, i.e.
with a water content in the range from 1 ppm to 0.1% by weight, which can be determined, for example, by Karl-Fischer titration.
Electrolyte (3) further comprises at least one electrolyte salt. Suitable electrolyte salts are, in particular, lithium salts. Examples of suitable lithium salts are LiPF6, LiBF4, LiCI04, LiAsF6,
___________________________________________ R (II) R1) (R2 3 /\
(III) R
where R1, R2 and R3 can be identical or different and are selected from among hydrogen and C1-C4-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, with R2 and R3 preferably not both being tert-butyl.
In particularly preferred embodiments, R1 is methyl and R2 and R3 are each hydrogen, or R1, R2 and R3 are each hydrogen.
Another preferred cyclic organic carbonate is vinylene carbonate, formula (IV).
V\
\¨/ (IV) The solvent or solvents is/are preferably used in the water-free state, i.e.
with a water content in the range from 1 ppm to 0.1% by weight, which can be determined, for example, by Karl-Fischer titration.
Electrolyte (3) further comprises at least one electrolyte salt. Suitable electrolyte salts are, in particular, lithium salts. Examples of suitable lithium salts are LiPF6, LiBF4, LiCI04, LiAsF6,
15 LiCF3S03, LiC(CnF2n+1S02)3, lithium imides such as LiN(CnF2n+1 S02)2, where n is an integer in the range from 1 to 20, LiN(SO2F)2, Li2SiF6, LiSbF6, LiAIC14 and salts of the general formula (CnF2n-F1S02)tYLi, where m is defined as follows:
t = 1, when Y is selected from among oxygen and sulfur, t = 2, when Y is selected from among nitrogen and phosphorus, and t = 3, when Y is selected from among carbon and silicon.
Preferred electrolyte salts are selected from among LiC(CF3S02)3, LiN(CF3S02)2, LiPF6, LiBF4, LiC104, with particular preference being given to LiPF6 and LiN(CF3S02)2.
In a preferred embodiment of the present invention, electrolyte (3) contains at least one flame retardant. Useful flame retardants may be selected from trialkyl phosphates, said alkyl being different or identical, triaryl phosphates, alkyl dialkyl phosphonates, and halogenated trialkyl phosphates. Preferred are tri-Ci-C4-alkyl phosphates, said Ci-C4-alkyls being different or identical, tribenzyl phosphate, triphenyl phosphate, C1-C4-alkyl di- C1-C4-alkyl phospho-nates, and fluorinated tri-C1-C4-alkyl phosphates, In a preferred embodiment, electrolyte (3) comprises at least one flame retardant selected from trimethyl phosphate, CH3-P(0)(OCH3)2, triphenylphosphate, and tris-(2,2,2-trifluoro-ethyl)phosphate.
Electrolyte (3) may contain 1 to 10% by weight of flame retardant, based on the total amount of electrolyte.
In an embodiment of the present invention, batteries according to the invention comprise one or more separators (4) by means of which the electrodes are mechanically separated. Suita-ble separators (4) are polymer films, in particular porous polymer films, which are unreactive toward metallic lithium. Particularly suitable materials for separators (4) are polyolefins, in particular film-forming porous polyethylene and film-forming porous polypropylene.
Separators (4) composed of polyolefin, in particular polyethylene or polypropylene, can have a porosity in the range from 35 to 45%. Suitable pore diameters are, for example, in the range from 30 to 500 nm.
In another embodiment of the present invention, separators (4) can be selected from among PET nonwovens filled with inorganic particles. Such separators can have a porosity in the
t = 1, when Y is selected from among oxygen and sulfur, t = 2, when Y is selected from among nitrogen and phosphorus, and t = 3, when Y is selected from among carbon and silicon.
Preferred electrolyte salts are selected from among LiC(CF3S02)3, LiN(CF3S02)2, LiPF6, LiBF4, LiC104, with particular preference being given to LiPF6 and LiN(CF3S02)2.
In a preferred embodiment of the present invention, electrolyte (3) contains at least one flame retardant. Useful flame retardants may be selected from trialkyl phosphates, said alkyl being different or identical, triaryl phosphates, alkyl dialkyl phosphonates, and halogenated trialkyl phosphates. Preferred are tri-Ci-C4-alkyl phosphates, said Ci-C4-alkyls being different or identical, tribenzyl phosphate, triphenyl phosphate, C1-C4-alkyl di- C1-C4-alkyl phospho-nates, and fluorinated tri-C1-C4-alkyl phosphates, In a preferred embodiment, electrolyte (3) comprises at least one flame retardant selected from trimethyl phosphate, CH3-P(0)(OCH3)2, triphenylphosphate, and tris-(2,2,2-trifluoro-ethyl)phosphate.
Electrolyte (3) may contain 1 to 10% by weight of flame retardant, based on the total amount of electrolyte.
In an embodiment of the present invention, batteries according to the invention comprise one or more separators (4) by means of which the electrodes are mechanically separated. Suita-ble separators (4) are polymer films, in particular porous polymer films, which are unreactive toward metallic lithium. Particularly suitable materials for separators (4) are polyolefins, in particular film-forming porous polyethylene and film-forming porous polypropylene.
Separators (4) composed of polyolefin, in particular polyethylene or polypropylene, can have a porosity in the range from 35 to 45%. Suitable pore diameters are, for example, in the range from 30 to 500 nm.
In another embodiment of the present invention, separators (4) can be selected from among PET nonwovens filled with inorganic particles. Such separators can have a porosity in the
16 range from 40 to 55%. Suitable pore diameters are, for example, in the range from 80 to 750 nm.
Batteries according to the invention can further comprise a housing which can have any shape, for example cuboidal or the shape of a cylindrical disk. In one variant, a metal foil configured as a pouch is used as housing.
Batteries according to the invention provide a very good discharge and cycling behavior, in particular at high temperatures (45 C or higher, for example up to 60 C) in particular with respect to the capacity loss.
Batteries according to the invention can comprise two or more electrochemical cells that combined with one another, for example can be connected in series or connected in parallel.
Connection in series is preferred. In batteries according to the present invention, at least one of the electrochemical cells contains at least one electrode according to the invention. Pref-erably, in electrochemical cells according to the present invention, the majority of the electro-chemical cells contain an electrode according to the present invention. Even more preferably, in batteries according to the present invention all the electrochemical cells contain electrodes according to the present invention.
The present invention further provides for the use of batteries according to the invention in appliances, in particular in mobile appliances. Examples of mobile appliances are vehicles, for example automobiles, bicycles, aircraft or water vehicles such as boats or ships. Other examples of mobile appliances are those which move manually, for example computers, es-pecially laptops, telephones or electric hand tools, for example in the building sector, espe-cially drills, battery-powered screwdrivers or battery-powered staplers.
The present invention is further illustrated by working examples.
Average particle diameters (D50) were determined by dynamic light scattering ("DLS"). Per-centages are % by weight unless specifically noted otherwise. All thermal processes were performed under an oxygen flow rate of 5 liters per minute in the furnace.
Step (a.1): A spherical Ni(OH)2 precursor was obtained by combining aqueous nickel sulfate solution (1.65 mol/kg solution) with an aqueous 25 wt.% NaOH solution and using ammonia as complexation agent. The pH value was set at 12.6. The freshly precipitated Ni(OH)2 was
Batteries according to the invention can further comprise a housing which can have any shape, for example cuboidal or the shape of a cylindrical disk. In one variant, a metal foil configured as a pouch is used as housing.
Batteries according to the invention provide a very good discharge and cycling behavior, in particular at high temperatures (45 C or higher, for example up to 60 C) in particular with respect to the capacity loss.
Batteries according to the invention can comprise two or more electrochemical cells that combined with one another, for example can be connected in series or connected in parallel.
Connection in series is preferred. In batteries according to the present invention, at least one of the electrochemical cells contains at least one electrode according to the invention. Pref-erably, in electrochemical cells according to the present invention, the majority of the electro-chemical cells contain an electrode according to the present invention. Even more preferably, in batteries according to the present invention all the electrochemical cells contain electrodes according to the present invention.
The present invention further provides for the use of batteries according to the invention in appliances, in particular in mobile appliances. Examples of mobile appliances are vehicles, for example automobiles, bicycles, aircraft or water vehicles such as boats or ships. Other examples of mobile appliances are those which move manually, for example computers, es-pecially laptops, telephones or electric hand tools, for example in the building sector, espe-cially drills, battery-powered screwdrivers or battery-powered staplers.
The present invention is further illustrated by working examples.
Average particle diameters (D50) were determined by dynamic light scattering ("DLS"). Per-centages are % by weight unless specifically noted otherwise. All thermal processes were performed under an oxygen flow rate of 5 liters per minute in the furnace.
Step (a.1): A spherical Ni(OH)2 precursor was obtained by combining aqueous nickel sulfate solution (1.65 mol/kg solution) with an aqueous 25 wt.% NaOH solution and using ammonia as complexation agent. The pH value was set at 12.6. The freshly precipitated Ni(OH)2 was
17 washed with water, sieved and dried at 120 C for 12 hours. p-CAM.1 was Ni(OH)2 with a D50 of 8 pm.
Manufacture of a comparative cathode active material, C-CAM.1:
Comparative cathode material C-CAM.1 (Lii.01Nio.95A10.005Coo.02Mno.02Zro.00502) was synthe-sized by mixing the precursor p-CAM.1 with the lithium source LiOH=H20 and dopant precur-sors (Co304, A1203, Zr(OH)4, Mn02) in appropriate stoichiometric ratios in a ball mill for 3 hours. The mixture was then poured into a zirconia crucible and heated from 25 C to 400 C
at 3 C/min, and then held at 400 C for 4 hours. The mixture was then heated from 400 C
to 692 C at 3 C/min, and then held at 692 C for 6 hours. Finally, the fixture was cooled from 692 C to 120 C at a cooling rate of more than 10 C/min and then transferred to a glovebox to obtain the comparative material C-CAM.1 with a d50 of 8 pm.
Step (b.2): the precursor p-CAM.1 was mixed with the lithium source Li0H-1-120 and the sources of Mg, M1 and M2: Mg(OH)2, A1203, Co304, Mn02, Zr(OH)4, W03) in appropriate stoi-chiometric ratios in a ball mill for 3 hours.
Step (c.2): The mixture obtained from (b.2) was then poured into a zirconia crucible and heated from 25 C to 400 C at 3 C/min, and then held at 400 C for 4 hours.
The mixture was then heated from 400 C to 675 C at 3 C/min, and then held at 675 C for 6 hours.
Finally, the fixture was cooled from 675 C to 120 C at a cooling rate of more than 10 C/min and transferred to a glovebox to obtain the inventive material CAM.2 with a d50 of 8 pm.
Inventive cathode material CAM .2 (Li =1.03oMgo.o20)N10.970Alo.005Coo.005Mno.oloZro.005Wo.00502) was obtained.
Electrode manufacture: Electrodes contained 94% CAM, 3% carbon black (Super C65) and 3% binder (polyvinylidene fluoride, Solef 5130). CAM, carbon black and binder were slurried in N-methyl-2-pyrrolidone and cast onto aluminum foil by doctor blade. After drying of the electrodes 6 h at 105 C in vacuo, circular electrodes were punched, weighed and dried at 120 C under vacuum for 12 hours before entering in an Ar filled glove box.
Half-Cell Electrochemical Measurements: Coin-type electrochemical cells, were assembled in an argon-filled glovebox. The positive 14 mm diameter (loading 8.0 0.5 mg cm-2) elec-trode was separated from the 0.58 thick Li foil by a glass fiber separator (Whatman GF/D).
An amount of 95 pl of 1 M LiPF6 in ethylene carbonate (EC): ethylmethyl carbonate (EMC), 3:7 by weight, was used as the electrolyte. Cells were galvanostatically cycled at a Maccor
Manufacture of a comparative cathode active material, C-CAM.1:
Comparative cathode material C-CAM.1 (Lii.01Nio.95A10.005Coo.02Mno.02Zro.00502) was synthe-sized by mixing the precursor p-CAM.1 with the lithium source LiOH=H20 and dopant precur-sors (Co304, A1203, Zr(OH)4, Mn02) in appropriate stoichiometric ratios in a ball mill for 3 hours. The mixture was then poured into a zirconia crucible and heated from 25 C to 400 C
at 3 C/min, and then held at 400 C for 4 hours. The mixture was then heated from 400 C
to 692 C at 3 C/min, and then held at 692 C for 6 hours. Finally, the fixture was cooled from 692 C to 120 C at a cooling rate of more than 10 C/min and then transferred to a glovebox to obtain the comparative material C-CAM.1 with a d50 of 8 pm.
Step (b.2): the precursor p-CAM.1 was mixed with the lithium source Li0H-1-120 and the sources of Mg, M1 and M2: Mg(OH)2, A1203, Co304, Mn02, Zr(OH)4, W03) in appropriate stoi-chiometric ratios in a ball mill for 3 hours.
Step (c.2): The mixture obtained from (b.2) was then poured into a zirconia crucible and heated from 25 C to 400 C at 3 C/min, and then held at 400 C for 4 hours.
The mixture was then heated from 400 C to 675 C at 3 C/min, and then held at 675 C for 6 hours.
Finally, the fixture was cooled from 675 C to 120 C at a cooling rate of more than 10 C/min and transferred to a glovebox to obtain the inventive material CAM.2 with a d50 of 8 pm.
Inventive cathode material CAM .2 (Li =1.03oMgo.o20)N10.970Alo.005Coo.005Mno.oloZro.005Wo.00502) was obtained.
Electrode manufacture: Electrodes contained 94% CAM, 3% carbon black (Super C65) and 3% binder (polyvinylidene fluoride, Solef 5130). CAM, carbon black and binder were slurried in N-methyl-2-pyrrolidone and cast onto aluminum foil by doctor blade. After drying of the electrodes 6 h at 105 C in vacuo, circular electrodes were punched, weighed and dried at 120 C under vacuum for 12 hours before entering in an Ar filled glove box.
Half-Cell Electrochemical Measurements: Coin-type electrochemical cells, were assembled in an argon-filled glovebox. The positive 14 mm diameter (loading 8.0 0.5 mg cm-2) elec-trode was separated from the 0.58 thick Li foil by a glass fiber separator (Whatman GF/D).
An amount of 95 pl of 1 M LiPF6 in ethylene carbonate (EC): ethylmethyl carbonate (EMC), 3:7 by weight, was used as the electrolyte. Cells were galvanostatically cycled at a Maccor
18 4000 battery cycler between 3.1 and 4.3 V at room temperature by applying the following C-rates until 70 % of the initial discharge capacity is reached at a certain discharge step:
Table 1: Electrochemical test procedure of the coin half cells.
Charge Discharge Cycles 1 - 2 0.1 C 0.1 C
Cycles 3 - 5 0.5 C+ CV* 0.2 C
Cycle 6 0.5 C + CV* 0.1 C
Cycle 7 0.5 C + CV* 0.2C
Cycle 8 0.5 C + CV* 0.5C
Cycle 9 0.5 C + CV 1C
Cycle 10 0.5 C + CV 2C
Cycle 11 0.5 C + CV* 0.1 C
Cycle 12 Resistance measurement (DCiR) Cycles 13 - 62 0.5 C + CV* 1.0 C
Cycle 63 0.5 C + CV* 0.1 C
Cycle 64 Resistance measurement (DCiR) Cycles 65 - 114 0.5 C + CV* 1.0 C
Cycle 115 0.5 C + CV* 0.1 C
Cycle 116 Resistance measurement After charging at the listed C-rates, all charge steps except the first were finished by a con-stant voltage step (CV*) for 1 h, or until the current reached 0.02C.
During the resistance measurement (conducted every 25 cycles at 25 C), the cell was charged at 0.1 C to reach 50% state of charge, relative to the previous discharge capacity.
To equilibrate the cell, a 30 min open circuit step followed. Finally, a 2.5 C
discharge current was applied for 30 s to measure the resistance. At the end of the current pulse, the cell was again equilibrated for 30 min in open circuit and further discharged at 0.1 C
to 3 .0 V.
To calculate the resistance, the voltage before applying the 2.5 C pulse current, V0s, and after 30 s of 2.5 C pulse current, V30 s, as well as the 2.5 C current value, (j in A), were tak-en. The resistance was calculated according to Eq. 3 (V: voltage, j: 2.5C
pulse current).
R = (V0s-V30s)/j (Eq. 3)
Table 1: Electrochemical test procedure of the coin half cells.
Charge Discharge Cycles 1 - 2 0.1 C 0.1 C
Cycles 3 - 5 0.5 C+ CV* 0.2 C
Cycle 6 0.5 C + CV* 0.1 C
Cycle 7 0.5 C + CV* 0.2C
Cycle 8 0.5 C + CV* 0.5C
Cycle 9 0.5 C + CV 1C
Cycle 10 0.5 C + CV 2C
Cycle 11 0.5 C + CV* 0.1 C
Cycle 12 Resistance measurement (DCiR) Cycles 13 - 62 0.5 C + CV* 1.0 C
Cycle 63 0.5 C + CV* 0.1 C
Cycle 64 Resistance measurement (DCiR) Cycles 65 - 114 0.5 C + CV* 1.0 C
Cycle 115 0.5 C + CV* 0.1 C
Cycle 116 Resistance measurement After charging at the listed C-rates, all charge steps except the first were finished by a con-stant voltage step (CV*) for 1 h, or until the current reached 0.02C.
During the resistance measurement (conducted every 25 cycles at 25 C), the cell was charged at 0.1 C to reach 50% state of charge, relative to the previous discharge capacity.
To equilibrate the cell, a 30 min open circuit step followed. Finally, a 2.5 C
discharge current was applied for 30 s to measure the resistance. At the end of the current pulse, the cell was again equilibrated for 30 min in open circuit and further discharged at 0.1 C
to 3 .0 V.
To calculate the resistance, the voltage before applying the 2.5 C pulse current, V0s, and after 30 s of 2.5 C pulse current, V30 s, as well as the 2.5 C current value, (j in A), were tak-en. The resistance was calculated according to Eq. 3 (V: voltage, j: 2.5C
pulse current).
R = (V0s-V30s)/j (Eq. 3)
19 The results show an improvement in the 1C rate and a higher stability after 140 (1C) and 141 (0,1C) cycles. In addition, the resistance growth is less compared to the comparative experi-ment.
Table 2: Results of electrochemical testing 1C Capacity / Cycle140/Cycle Cycle141/Cycle13 50% SoC
after mAh/g 15 (1C)/ % (0.1C) / % 142 cycles (Q=cm2) C-CAM.1 177.1 72.1 80.2 65.8 CAM.2 183 78.9 82.8 37.4 SoC: state of charge
Table 2: Results of electrochemical testing 1C Capacity / Cycle140/Cycle Cycle141/Cycle13 50% SoC
after mAh/g 15 (1C)/ % (0.1C) / % 142 cycles (Q=cm2) C-CAM.1 177.1 72.1 80.2 65.8 CAM.2 183 78.9 82.8 37.4 SoC: state of charge
Claims (11)
1. Particulate material of the composition (LiaMgb)1+x(NicM1A4201-x02 wherein M1 is selected from Ti, Zr, Nb, Mo, and W, and combinations of at least two of the aforementioned, M2 is selected from Al, Co and Mn and combinations of at least two of the aforemen-tioned, a : b is in the range of from 100:1 to 400:1, and a + b = 1, c : d is in the range of from 40:1 to 250:1, and c : e is in the range of from 12:1 to 50:1, and c + d + e = 1, total molar ratio of (Li + Mg) to (Ni + M1+ M2) is in the range of from 1:1 to 1.05:1, 0.00 x 0.05, wherein said particulate material has an average particle diameter (D50) in the range of from 2 to 20 pm.
2. Particulate material according to claim 1 wherein said material comprises a combina-tion of metals according to general formula (l) (NicM1dM2e) (1) with M2 being selected from Mn and Co, c being in the range of from 0.95 to 0.995, d being in the range of from 0.002 to 0.04, e being in the range of from 0.002 to 0.02, and c + d + e = 1.
3. Particulate material according to claim 1 or 2 wherein M1 is selected from Ti, Zr and W, and combinations of at least two of the aforementioned.
4. Particulate material according to any of claims the number of metals other than Ni, Mg and Li is at least three and at most five.
5. Particulate material according to any of the preceding claims wherein said material has an integral peak width 2nd charge1PW4.1 ¨ 4.25 V in the differential capacity plot (dQ)/(dV) of at least 25 mV between 4.1 and 4.25 V in the second charge cycle at 0.2 C-rate.
6. Particulate material according to any of the preceding claims wherein said material is coated with a metal oxide.
7. Process for manufacturing a particulate material according to any of claims 1 to 6 wherein said process comprises the following steps:
(a) providing a particulate nickel hydroxide, nickel (II) oxide or nickel oxyhydroxide, (b) mixing said nickel oxide/hydroxide or oxyhydroxide with compounds of Mg, of M1 and M2, and with a source of lithium, (c) treating the mixture obtained from step (b) thermally.
(a) providing a particulate nickel hydroxide, nickel (II) oxide or nickel oxyhydroxide, (b) mixing said nickel oxide/hydroxide or oxyhydroxide with compounds of Mg, of M1 and M2, and with a source of lithium, (c) treating the mixture obtained from step (b) thermally.
8. Process according to claim 7 wherein step (c) is performed at a maximum temperature in the range of from 650 to 750 C.
9. Cathode containing (A) at least one particulate material according to any of claims 1 to 6, (B) carbon in electrically conductive form, (C) a binder material.
10. Cathode according to claim 9 containing (A) 80 to 98 % by weight cathode active material, (B) 1 to 17 % by weight of carbon, (C) 3 to 10 % by weight of binder material, percentages referring to the sum of (A), (B) and (C).
11. Electrochemical cell containing at least one cathode according to claim 9 or 10.
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EP21183567 | 2021-07-02 | ||
EP21183567.3 | 2021-07-02 | ||
PCT/EP2022/066302 WO2023274726A1 (en) | 2021-07-02 | 2022-06-15 | Particulate material, method for its manufacture and use |
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EP (1) | EP4364218A1 (en) |
KR (1) | KR20240027628A (en) |
CN (1) | CN117597796A (en) |
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ES2915724T3 (en) * | 2012-04-05 | 2022-06-24 | Tosoh Corp | Combined trimanganese tetraoxide metal-containing particles and their production process |
KR102561910B1 (en) * | 2015-05-22 | 2023-08-01 | 내셔날 인스티튜트 오브 어드밴스드 인더스트리얼 사이언스 앤드 테크놀로지 | Cathode material, lithium secondary battery using this as a cathode |
WO2020094716A1 (en) * | 2018-11-09 | 2020-05-14 | Basf Corporation | Process for making lithiated transition metal oxide particles, and particles manufactured according to said process |
US20220212950A1 (en) * | 2019-06-28 | 2022-07-07 | Basf Se | Lithium nickel oxide particulate material, method for its manufacture and use |
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- 2022-06-15 EP EP22734271.4A patent/EP4364218A1/en active Pending
- 2022-06-15 KR KR1020237045358A patent/KR20240027628A/en unknown
- 2022-06-15 WO PCT/EP2022/066302 patent/WO2023274726A1/en active Application Filing
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WO2023274726A1 (en) | 2023-01-05 |
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